CN102875311B - Method for preparing hexene by olefin metathesis in fluidized bed - Google Patents
Method for preparing hexene by olefin metathesis in fluidized bed Download PDFInfo
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- CN102875311B CN102875311B CN201110193427.4A CN201110193427A CN102875311B CN 102875311 B CN102875311 B CN 102875311B CN 201110193427 A CN201110193427 A CN 201110193427A CN 102875311 B CN102875311 B CN 102875311B
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Abstract
The invention relates to a method for preparing hexene by olefin metathesis in a fluidized bed, mainly solving the problem of rapid coking and deactivation of catalyst and low yield of hexene. The method disclosed herein is characterized by using C4 as a raw material and contacting the raw material with a fluid catalyst to react to generate a flow containing hexene under the reaction conditions comprising a reaction temperature of 320-480 DEG C, a reaction pressure being 0-1MPa based on absolute pressure, and a weight hourly space velocity being 6-25h<-1>, and the catalyst used herein is a tungsten-based fluid catalyst. The method disclosed herein well solves the problems and can be applied for the industrial production of preparing hexene by olefin metathesis.
Description
Technical field
The present invention relates to a kind of method for fluidized-bed olefin metathesis hexene processed.
Background technology
As a kind of olefin product of high added value, the synthetic of hexene paid attention to very much.The conventional preparation method of current industrial hexene generates 1-hexene by ethylene polymerization, and the catalyzer of employing is alkylating metal catalyst.By olefin metathesis technology, C4 conversion of olefines low value-added relative surplus can be become to hexene and the ethene of high added value.
Olefin metathesis (Olefin metathesis) is a kind of conversion of olefines process.Under the effect at transition-metal catalyst (as W, Mo, Re etc.), the fracture of the two keys of C=C and formation again in alkene, thus can obtain new olefin product.We can represent simply from following reaction formula the dismutation of alkene:
R in reaction formula
1, R
2, R
3, R
4represent respectively different alkyl or hydrogen atom.If wherein the disproportionation reaction of same alkene (suc as formula 1) is called self disproportionation (self-metathesis); Disproportionation reaction (formula 2) between different alkene is called cross disproportionation (cross-metathesis).
The control of self disproportionation reaction of 1-butylene is the most key, because 1-butylene double bond isomerization reaction generates 2-butylene, and 1-butylene and 2-butylene cross disproportionation cause hexene optionally to reduce, so the key of this technology is to suppress in raw material 1-butylene at the double-bond isomerization of catalyst surface.
WO02059066 has reported the automatic disproportionation technology of 1-butylene.The catalyzer that this technology adopts is that Tungsten oxide 99.999 loads on silicon oxide, and at the temperature of 200 DEG C～350 DEG C, 1-butylene self disproportionation generates ethene and 3-hexene.3-hexene is converted into 1-hexene in isomerization reaction subsequently.This patent points out, adds 2-amylene and be conducive to 3-hexene in product and optionally improve in reactant.
WO03076371A1 has reported the technology of preparing propylene and hexene taking butylene as raw material.The catalyzer that this technology adopts is that Tungsten oxide 99.999 loads on silicon oxide, and temperature of reaction is 343 DEG C, and reaction pressure is 5bar.
Method in above document, in the time of the reaction for olefin metathesis hexene processed, all exists the quick coking and deactivation of catalyzer to make catalyst life short, and the low problem of hexene yield.
Summary of the invention
Technical problem to be solved by this invention is in prior art, to exist the quick coking and deactivation of catalyzer to cause work-ing life short, and the problem that hexene yield is low provides a kind of new method for fluidized-bed olefin metathesis hexene processed.The method has catalyzer long service life, the advantage that hexene yield is high.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method for fluidized-bed olefin metathesis hexene processed, taking carbon four as raw material, is 320～480 DEG C in temperature of reaction, reaction pressure is counted 0～1MPa with absolute pressure, and weight space velocity is 6～25 hours
-1condition under, fluid catalyst contact reacts in raw material and fluidized-bed generates the logistics containing hexene, wherein fluid catalyst used comprises following component by weight percentage:
A) 0.08～20% Tungsten oxide 99.999;
B) 20～80% be selected from least one of MCM series, SBA series, MSU series mesopore molecular sieve carrier;
C) 10～60% be selected from least one binding agent in aluminium colloidal sol, silicon sol or silicon-aluminum sol.
In technique scheme, the preferable range of temperature of reaction is 380～450 DEG C, and the preferable range of reaction pressure is 0.4～0.6MPa, and the preferable range of weight space velocity is 8～15 hours
-1, the preferable range of Tungsten oxide 99.999 consumption is 2～16%; The preferred version of MCM series mesopore molecular sieve is MCM-48; The preferred version of SBA series mesopore molecular sieve is SBA-15; The preferred version of MSU series mesopore molecular sieve is MSU-x; The preferred version of binding agent is silicon sol.
The preparation technology of catalyzer comprises that slurrying, spraying are shaped, roasting three steps.Conventionally first mesopore molecular sieve carrier is added to appropriate deionized water and soak, add active ingredient tungsten source simultaneously, then stir with high-shear making beating, then add the binding agent of required amount.Intensity for catalyzer and performance, the reinforced order of various raw materials changes the difference there is no greatly, thereby can regulate arbitrarily as required reinforced order.Prepared like this slurry is uniform suspension, generally can place 24 hours and not obvious layering.
Conventionally the solid content of slurry is 25～45%, for reducing evaporation of water amount, reduces energy consumption, and solid content should be tried one's best high.Slurry is under 600 DEG C of inlet temperatures, 350 DEG C of conditions of outlet, and spray drying granulation moulding, must be containing the microsphere particle of a small amount of water, then 550 DEG C of roastings 4 hours in retort furnace.
The microsphere particle catalyzer making is dried to obtain catalyst sample.Sample, by standard test abrasion index, bulk density and granularity, is tested to its physical and chemical indexes.
Prepared catalyzer is the spheroidal particle of 30～100 microns, and median size is 60 microns, bulk density 0.6～0.8 kg/liter, and abrasion index is 0.5～0.7% hour
-1.
In the present invention, tungsten source can be the one in wolframic acid, sodium wolframate, ammonium tungstate, ammonium metawolframate, and tungsten source is ammonium metawolframate preferably.
Mesoporous material has a kind of type material of nano level homogeneous pore passage structure and bigger serface, is a kind of good support of the catalyst, by load or direct synthesizing active ingredient being introduced to mesoporous carrier, can provide catalyzed reaction needed active sites.Compared with conventional carrier, the active ingredient dispersity on mesoporous material is better, and reactant is more abundant with contacting of active centre, is especially applicable to the reaction system of large flow, high-speed.
Catalyzer prepared by technique scheme is for fluidized-bed olefin dismutation reaction, and the embodiment of the present invention is that carbon four disproportionations generate hexene.Reaction conditions is as follows: in fluidized bed reactor, temperature of reaction is 320～480 DEG C, and reaction pressure is counted 0～1MPa with absolute pressure, and the mass space velocity of carbon four is 6～25 hours
-1.
In such scheme, carbon four raw materials can be the mixture of butene-1, butene-2 or butane, or from the C-4-fraction of steam cracking device.
The present invention is by adopting the molecular sieve carrier of high-ratio surface, and mesopore molecular sieve aperture is 2.7～6.4 nanometers, and specific surface area is 600～1250 meters
2/ gram, improve the dispersity of Tungsten oxide 99.999 at carrier, make the catalyzer of preparation there is higher reactive behavior and hexene selectivity, ensure the good physical strength of catalyzer simultaneously.The present invention adopts fluid catalyst as catalysts, in reaction, amount of heat can be withdrawn to reactor, has improved the work-ing life of catalyzer.Adopt method of the present invention, in fluidized-bed reactor, temperature of reaction is 320～480 DEG C, and reaction pressure is counted 0～1MPa with absolute pressure, carbon four weight space velocity be 6～25 hours
-1under condition, by catalyzer and reaction raw materials contact reacts, the transformation efficiency of its butylene can reach 65%, the weight yield of hexene can reach 28%, higher by 3% than react the yield obtaining with fixed bed catalyst, the life-span of catalyzer can reach 900 hours, and the life-span of fixed bed catalyst is only 400 hours, life one times, obtained good technique effect.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
Produce MCM-48 mesopore molecular sieve by ordinary method, aperture is 3.4 nanometers, and specific surface area is 1213 meters
2/ gram.
1 kilogram of MCM-48 is added in 2 kilograms of deionized waters and soaked 10 minutes, pull an oar and add containing 200 grams of 63 grams of ammonium metatungstate solutions after 10 minutes, finally add 200 grams of silicon sol (silica content 40%) making beating 15 minutes, obtain the slurry of 40% solid content.This slurry, 600 DEG C of import air temperatures, is gone out to 350 DEG C of conditions of one's intention as revealed in what one says and is spray dried to shape, then catalyzer is made in roasting for 4 hours at 550 DEG C of retort furnaces, the median size of catalyzer is 60 microns, the bulk density of detecting catalyst and abrasion index, the results list 1.
30 grams of catalyzer are arranged in the fluidized-bed reactor of Φ 30mm, with etherificate C
4for raw material is at air speed WHSV10 hour
-1, under 400 DEG C and 0.5MPa condition, check and rate catalyst performance, the results list 2.
[embodiment 2～6]
With the identical preparation process of embodiment 1, only change different components ratio and mesopore molecular sieve, obtain different catalysts, catalyzer median size is all 60 microns, the bulk density of detecting catalyst and abrasion index, the results list 1.
30 grams of catalyzer are arranged in the fluidized-bed reactor of Φ 30mm, with etherificate C
4for raw material is at air speed WHSV10 hour
-1, under 400 DEG C and 0.5MPa condition, check and rate catalyst performance, the results list 2.
The physical data of table 1 different catalysts
The evaluation result of table 2 different catalysts
| Example | Molecular sieve title | Butene conversion (%) | Hexene yield (%) | Life-span (h) |
| 1 | MCM-48 | 65.5 | 28.4 | 910 |
| 2 | MCM-41 | 64.0 | 27.7 | 840 |
| 3 | SBA-15 | 67.8 | 29.2 | 930 |
| 4 | SBA-3 | 66.3 | 28.9 | 920 |
| 5 | MSU-x | 64.5 | 26.3 | 830 |
| 6 | MSU-V | 67.8 | 28.1 | 940 |
[embodiment 7～11]
With embodiment 1 catalyzer, change the appraisal result list 3 of different technology conditions
Catalyst activity appraisal result under table 3 different technology conditions
Note: pressure is in absolute pressure.
[comparative example 1]
Taking 63 grams of ammonium metawolframates adds in 2 kilograms of deionized waters, after being uniformly dissolved, pour 1 kilogram of MCM-48 into, add 200 grams of silicon sol uniform stirring simultaneously, after stirring for some time, add 1% field mountain valley with clumps of trees and bamboo powder, kneading, extrusion, dry after roasting 4 hours at 550 DEG C, obtain catalyzer finished product.
30 grams of catalyzer are arranged in the fixed-bed reactor of Φ 30mm, with etherificate C
4for raw material is at air speed WHSV10 hour
-1, under 400 DEG C and 0.5MPa condition, check and rate catalyst performance, evaluation result is as shown in table 4.
[comparative example 2]
With the identical preparation process of comparative example 1, change carrier and different components ratio and obtain different catalysts.
30 grams of catalyzer are arranged in the fixed-bed reactor of Φ 30mm, with etherificate C
4for raw material is at air speed WHSV10 hour
-1, under 400 DEG C and 0.5MPa condition, check and rate catalyst performance, the results list 4.
[comparative example 3]
1 kilogram of conventional silicon oxide is added in 2 kilograms of deionized waters and soaked 10 minutes, pull an oar and add containing 200 grams of 63 grams of ammonium metatungstate solutions after 10 minutes, finally add 200 grams of silicon sol (silica content 40%) making beating 15 minutes, obtain the slurry of 40% solid content.This slurry, 600 DEG C of import air temperatures, is gone out to 350 DEG C of conditions of one's intention as revealed in what one says and is spray dried to shape, then catalyzer is made in roasting for 4 hours at 550 DEG C of retort furnaces, the median size of catalyzer is 60 microns.
30 grams of catalyzer are arranged in the fluidized-bed reactor of Φ 30mm, with etherificate C
4for raw material is at air speed WHSV10 hour
-1, under 400 DEG C and 0.5MPa condition, check and rate catalyst performance, the results list 4.
[comparative example 4]
With the identical preparation process of comparative example 3, only change different components ratio and obtain different catalysts.
30 grams of catalyzer are arranged in the fluidized-bed reactor of Φ 30mm, with etherificate C
4for raw material is at air speed WHSV10 hour
-1, under 400 DEG C and 0.5MPa condition, check and rate catalyst performance, the results list 4.
Table 4 activity rating of catalyst result
Claims (8)
1. the method for fluidized-bed olefin metathesis hexene processed, taking carbon four as raw material, it is 320～480 DEG C in temperature of reaction, reaction pressure is counted 0～1MPa with absolute pressure, weight space velocity is to be greater than 8 to be less than or equal under the condition of 15 hours-1, fluid catalyst contact reacts in raw material and fluidized-bed generates the logistics containing hexene, and wherein fluid catalyst used comprises following component by weight percentage:
A) 0.08～20% Tungsten oxide 99.999;
B) 20～80% be selected from least one of MCM series, SBA series, MSU series mesopore molecular sieve carrier;
C) 10～60% be selected from least one binding agent in aluminium colloidal sol, silicon sol or silicon-aluminum sol.
2. the method for fluidized-bed olefin metathesis hexene processed according to claim 1, is characterized in that temperature of reaction is 360～450 DEG C.
3. the method for fluidized-bed olefin metathesis hexene processed according to claim 1, is characterized in that reaction pressure counts 0.4～0.6MPa with absolute pressure.
4. the method for fluidized-bed olefin metathesis hexene processed according to claim 1, is characterized in that the consumption of Tungsten oxide 99.999 is 2～16% by weight percentage.
5. the method for fluidized-bed olefin metathesis hexene processed according to claim 1, it is characterized in that being selected from MCM series mesopore molecular sieve is MCM-48.
6. the method for fluidized-bed olefin metathesis hexene processed according to claim 1, it is characterized in that being selected from SBA series mesopore molecular sieve is SBA-15.
7. the method for fluidized-bed olefin metathesis hexene processed according to claim 1, it is characterized in that being selected from MSU series mesopore molecular sieve is MSU-x.
8. the method for fluidized-bed olefin metathesis hexene processed according to claim 1, is characterized in that binding agent is selected from silicon sol.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6583329B1 (en) * | 1998-03-04 | 2003-06-24 | Catalytic Distillation Technologies | Olefin metathesis in a distillation column reactor |
| CN1589968A (en) * | 2003-09-03 | 2005-03-09 | 中国石油化工股份有限公司 | Olefin disproportionation catalyst |
| CN1827210A (en) * | 2006-04-19 | 2006-09-06 | 中国科学院大连化学物理研究所 | Catalyst for preparing propylene by disproportionating propylene and method for preparing the same |
| CN102464548A (en) * | 2010-11-17 | 2012-05-23 | 中国石油化工股份有限公司 | Method for preparing propylene by disproportionating fluidized bed olefin |
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2011
- 2011-07-12 CN CN201110193427.4A patent/CN102875311B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6583329B1 (en) * | 1998-03-04 | 2003-06-24 | Catalytic Distillation Technologies | Olefin metathesis in a distillation column reactor |
| CN1589968A (en) * | 2003-09-03 | 2005-03-09 | 中国石油化工股份有限公司 | Olefin disproportionation catalyst |
| CN1827210A (en) * | 2006-04-19 | 2006-09-06 | 中国科学院大连化学物理研究所 | Catalyst for preparing propylene by disproportionating propylene and method for preparing the same |
| CN102464548A (en) * | 2010-11-17 | 2012-05-23 | 中国石油化工股份有限公司 | Method for preparing propylene by disproportionating fluidized bed olefin |
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